CN1101891A - Process for the catalytic partial oxidation of hydrocarbons - Google Patents

Process for the catalytic partial oxidation of hydrocarbons Download PDF

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CN1101891A
CN1101891A CN94106477A CN94106477A CN1101891A CN 1101891 A CN1101891 A CN 1101891A CN 94106477 A CN94106477 A CN 94106477A CN 94106477 A CN94106477 A CN 94106477A CN 1101891 A CN1101891 A CN 1101891A
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catalyzer
requirement
gas
aforesaid right
hydrocarbon feed
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CN1039698C (en
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L·L·G·亚考伯
P·W·乐德诺
K·A·万克曼
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Shell Internationale Research Maatschappij BV
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1023—Catalysts in the form of a monolith or honeycomb
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1029—Catalysts in the form of a foam
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A process for the catalytic partial oxidation of a hydrocarbon feedstock comprises contacting a feed comprising a hydrocarbon feedstock and an oxygen-containing gas at elevated pressure and a temperature of at least 950 DEG C with a catalyst comprising as a catalytically active metal rhodium, iridium or ruthenium.

Description

Process for the catalytic partial oxidation of hydrocarbons
The present invention relates to the process for catalystic partial oxidation of hydrocarbon, particularly prepare the method for the mixture of carbon monoxide and hydrogen from the light hydrocarbon in methane, Sweet natural gas, casing-head gas or other source.
In the presence of catalyzer, will be as the hydrocarbon partial oxidation of methane or Sweet natural gas, be the important preparation method of this area carbon monoxide and hydrogen mixture of being referred to as synthetic gas.So the synthetic gas of preparation can change into many value products, as preparing medium boiling range hydrocarbon fuel with the Fischer-Tropsch synthesis method, preparation chloroflo, lubricating base oil or methyl alcohol.
Best process for catalystic partial oxidation can be in elevated pressure as 30 crust, and in very high air speed according to appointment 1,000, the 000Nl/l/h high productivity makes carbon monoxide and hydrogen.Owing to the thermodynamics reason, for high yield under these operational conditions obtains-carbonoxide and hydrogen, portion's oxidation style need at high temperature be carried out.But, under the desired high temperature of this operation, be difficult to satisfy commercial run keeps high reactivity and highly selective in the longer operating time to catalyzer requirement.
Many bibliographical informations have been arranged the particularly catalyzing part oxidation experiment of methane of hydrocarbon, they have adopted various catalyzer.But these experiments are most of to be carried out under condition as mild as a dove, or carries out under the condition that is unsuitable for the industrialization catalyzing part oxidation fully.
Therefore, european patent application discloses the process for catalystic partial oxidation that the 0 303 No. 438 (EP-A-0 303 438) disclose hydrocarbon feed, wherein the gaseous mixture of hydrocarbon feed, oxygen or oxygenous gas and non-imposed water vapor is introduced the catalyzing part oxidation zone, and remain on this regional catalyzer and contact.The catalyzer that is used for this method can comprise many catalytic active component, as palladium, platinum, rhodium, iridium, osmium, ruthenium, nickel, chromium, cobalt, cerium, lanthanum and their mixture.In addition, EP-A-0 303 438 also claims, usually the material that is considered to not have catalytic activity is useful as catalysts also, for example as the refractory matter oxide compound of trichroite, mullite, aluminium titanates mullite (mullite aluminium titanate), zirconium white spinel and aluminum oxide.Catalyzer can take various forms, for example inner accumulation wavy metal plate or the gauze that extends passage that form.But, the EP-A-0 303 438 preferred catalyzer that use whole shape.
European patent the 0 262 No. 947 (EP-B-0 262 947) discloses the method that partial oxidation of hydrocarbons produces hydrogen, wherein with the mixture injection-integer catalyzer of hydrocarbon and oxygen.EP-B-0 262 947 disclosed catalyzer comprise platinum and the chromated oxide that is stated from the refractory matter solid.
D.A.Hickmam and L.D.Schmidt(" Synthesis Gas Formation by Direct Oxidation of Methane over Pt Monoliths ", Journal of Catalysis 138,1992, the 267-282 page or leaf) done the experiment that there is the lower section oxidizing of methylene in catalyzer, catalyzer or contain platinum or contain rhodium.The form of the catalyzer that uses is as the polycrystalline platinum foil or be stated from rhodium or platinum on the ceramic foam carrier.Partial oxidation reaction is basically barometric point and 600-1500K(337-1237 ℃) under carry out.
A.T.Ashcroft etc. (" Selective oxidation of methane to synthesis gas using trsnsition metal catalysts ", Nature, vol 344, No6264,319-321 page or leaf, March 22 nineteen ninety) method that methane portion oxidation is become synthetic gas in the presence of various ruthenium-containing catalysts is disclosed.The purpose of these experiments is in order to prove that method for partical oxidation can carry out under mild conditions and low temperature.Therefore, these are tested 40, the low gas hourly space velocity of 000/hr, and 1 atmospheric pressure carries out under about 775 ℃ temperature.Have only an experiment to adopt elevated pressure.But, when adopting high pressure, used excessive greatly methane, to avoid explosion hazard.
P.D.F.Vernon etc. (" Partial Oxidation of methane to Synthesis Gas ", Catalysis Lett ers 6(1990) 181-186 page or leaf) some experiments is disclosed, wherein used the catalyzer that comprises nickel, ruthenium, rhodium, palladium, iridium or platinum, this catalyzer or be stated from the aluminum oxide, or be present in the blended oxide precursor.These experiments also only limit to adopt the process for catalystic partial oxidation of mild conditions, have selected a cover mild reaction conditions: 1 atmospheric pressure, 40, the gas hourly space velocity of 000/hr, 1050K(777 ℃) temperature and methane/oxidation ratio of 2.0.Based on this, studied every kind of effects of operation conditions.Studies show that cold operation has certain benefit, but this only pressure be about be only under 1 normal atmosphere practical.The author is also at " Partial Oxidation of Methane to Synthesis Gas; and Carbon Dioxide as an Oxidising Agent for Methane Conversion ", Catalysis Today 13(1992) has reported identical experiment among the 417-426.
(" Catalytic Conversion of Methane to Synthesis Gas over Europium Iridate, Eu such as R.H.Jones 2Lr 2O 7", Catalysis Letters 8(1991) 169-174) reported use europium iridium pyrrhite Eu 2Ir 2O 7The selectivity partial oxidation of methane.1 atmospheric pressure and 873K(600 ℃) studied this reaction under the mild conditions of temperature.
J.K.Hockmuth(" Catalytic Partial Oxidation of Methane over a monolith Supported Catalyst ", Applied Catalysis B:Environmental, 1(1992) 89-100) reported the catalyzing part oxidation of the methane that uses catalyzer, this catalyzer comprises and is stated from green stone platinum and palladium composition on the whole.
United States Patent (USP) the 5th, 149,464(us-A-5,149,464) purpose is the method that optionally methane oxidation is become carbon monoxide and hydrogen, it achieves the goal by at about 650 ℃-900 ℃ reactant gas mixtures is contacted with solid catalyst, and this catalyzer generally is selected from following catalyzer:
A), general formula is MxM 1 yThe catalyzer of Oz, wherein:
M is the element of at least a Mg of being selected from, B, Al, Ln, Ga, Si, Ti, Zr and Hf; Ln is at least a lanthanon;
M 1Be d track shielding (d-block) transition metal, and the ratio of x/y, y/z and (x+y)/z is separate, all is between 0.1 to 8;
B) oxide compound of d track shielding transition metal;
C) the d track that is stated from the refractory matter carrier shields transition metal;
D) under reaction conditions or under non-oxide condition, heat a) or b) catalyzer that forms.
US-A-5,149, d track shielding transition metal described in 464 is selected from the metal that ordination number is 21-29,40-47 and 72-79, i.e. metal scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold.US-A-5,149,464 claim that preferred metal is periodic table of elements VIII family metal, i.e. iron, osmium, cobalt, rhenium, iridium, palladium, platinum, nickel and ruthenium.
US-A5, the method for describing in 149,464 is preferably carried out under 700 ℃-800 ℃ under 650 ℃-900 ℃.US-A-5,149,464 have described a series of experiment, wherein tested the different catalysts that comprises VIII family metal, catalyzer comprises ruthenium oxide, praseodymium/ru oxide, pyrrhite, be stated from ruthenium on the aluminum oxide, be stated from rhodium on the aluminum oxide, be stated from the palladium on the aluminum oxide, is stated from platinum, nickel/aluminum oxide, uhligite and nickel oxide on the aluminum oxide.
The relevant disclosure that is used for the catalyzer of process for catalystic partial oxidation also sees the open WO92/11199 of international patent application.WO92/11199 describes the experiment of wherein having used catalyzer in detail, and catalyzer comprises iridium, palladium, ruthenium, rhodium, nickel and the platinum that is stated from the aluminum oxide.All experiments are carried out under mild operating conditions, and typical operation conditions is: pressure 1 normal atmosphere, temperature 1050K(777 ℃), gas hourly space velocity is about 20,000/hr.WO/11199 also claims, the research well afoot of catalyzer prolongs life, but most catalyzer can only be at 80 hours, also may be in the longer time non-inactivation.
As mentioned above, industrial application requiring process for catalystic partial oxidation should be operated under elevated pressure, thereby its service temperature requires to be higher than the temperature in the above-mentioned document.When evaluation was used for the catalyzer of commercial run, a most important index was the stability of this catalyzer under operational condition.The mild conditions that the described experiment of prior art is adopted can not disclose the stability of various catalyst compositions under the desired critical operation condition of industrial implementation down.Under these critical operation conditions, be surprisingly found out that the stability of the disclosed VIII of prior art family metal catalyst has significant difference.Be the most astoundingly, the rule of claiming with WO92/11199 is opposite, finds under industrial enforceable condition, the catalyzer that contains rhodium, iridium or ruthenium with the stability of selectivity and active expression all apparently higher than other VIII family metal catalyst.
Therefore, the invention provides the process for catalystic partial oxidation of hydrocarbon feed, this method comprises, under elevated pressure, at least 950 ℃, the charging that comprises hydrocarbon feed and oxygenous gas contacted with the catalyzer that contains catalytically-active metals rhodium, iridium or ruthenium.
The inventive method can be used for preparing from any gaseous state or low boiling hydrocarbon the mixture of carbon monoxide and hydrogen.This discover method is particularly suitable for the light hydrocarbon in partial oxidation methane, Sweet natural gas, casing-head gas or other source.
Make hydrocarbon feed and oxygenous gas reaction.Air is suitable for use as oxygenous gas.But the oxygen that preferably uses substantially pure is as oxygenous gas.Need not handle a large amount of noble gases like this, the nitrogen when being used as oxygenous gas as air.Charging can contain water vapor non-imposedly.
The consumption of hydrocarbon feed and oxygen-containing gas should make charging have suitable oxygen/carbon ratio in the charging.Oxygen/carbon ratio is preferably 0.3-0.8, more preferably 0.45-0.75." oxygen/carbon ratio " means oxygen molecule (O 2Ratio with carbon atom in the hydrocarbon feed.Oxygen/carbon ratio is preferably 0.45-0.65, and preferred especially oxygen/carbon ratio is about stoichiometric number 0.5.As exist in the charging water vapor, water vapor/carbon ratio be preferably from greater than 0.0 to 3.0,0.0-2.0 more preferably.With before catalyzer contacts, preferably make hydrocarbon feed, oxygen-containing gas and water vapor (as existing) thorough mixing.
The inventive method is in elevated pressure, and promptly pressure is apparently higher than normal atmosphere operation down.This method can operated to reaching under 150 crust.Working pressure is preferably the 3-100 crust, more preferably the 10-75 crust.
Under the condition of high voltage that the inventive method adopted, be the high conversion that obtains wishing, charging is contacted with catalyzer at elevated temperatures.Therefore, the inventive method is operated under at least 950 ℃ temperature.The preferred 950-1300 of service temperature ℃, more preferably 950-1200 ℃.With before catalyzer contacts, be favourable with feeding preheating.
In the methods of the invention, the charging of available any suitable air speed, and high gas hourly space velocity is preferred.Therefore, the typical air speed of the inventive method is about 20,000 ,-Yue 50,000,000Nl/l/hr.More preferably from about 50,000-is about 20,000,000Nl/l/hr.Shi Yi air speed is 500 especially, 000-10,000,000Nl/l/hr.
The catalyzer that is used for the inventive method contains the metal of selected from rhodium as catalytic active component, iridium, ruthenium.The catalyzer that especially preferably contains rhodium.
Preferably catalytically-active metals is stated from the carrier.Suitable solid support material is known in this area, and it comprises the refractory matter oxide compound, as silicon-dioxide, aluminum oxide, titanium dioxide, zirconium white and their mixture.Available method well known in the art is deposited on catalytically-active metals on the refractory matter oxide carrier.With metal deposition optimum method on carrier is pickling process, and this method normally makes solid support material contact with the solution of the compound of catalytically-active metals, subsequent drying and roasting gained solid support material.
For the inventive method, can use any suitable reaction unit that charging is contacted with catalyzer.A kind of suitable reaction unit is a fluidized-bed, wherein uses catalyzer with particle form.The preferred reaction unit of the inventive method is a fixed-bed reactor, wherein keeps catalyzer with stationary installation in reaction.In fixed bed device, catalyzer also can use with particle form.In addition, but also show bubble of catalyzer, and it for example can flood the ceramic foam preparation by aforesaid method.The suitable ceramic foam that is used to prepare this catalyzer comprises the foams of those 30-150 hole/inches (12-60 hole/centimetre).Other form of catalyzer also comprises refractory matter oxide compound, honeycomb one-piece construction and wire netting, and catalytically-active metals is deposited on honeycomb one-piece construction or the wire netting.
In the inventive method preferred embodiment, charging is contacted with catalyzer in the fixed bed device that remains on high tortuosity degree (tortuosity)." tortuosity degree " is the generic term of this area, when being used for fixing catalyst bed, it be defined as gas stream cross this passage length and the ratio of short lines passage length of process by this.Therefore, the integrally-built tortuosity degree of honeycomb is 1.0.In the present invention, " high tortuosity degree " device is meant that particularly the tortuosity degree is at least 1.1 device than the big device of the integrally-built tortuosity degree of honeycomb.The tortuosity degree of granules of catalyst fixed bed is about 1.5, and ceramic foam can be made and has 3.0-4.0 or how high tortuosity degree.Generally speaking, the tortuosity degree of fixed bed device is preferably 1.1 to about 10.0, more preferably to about 5.0.Optimum tortuosity degree scope is 1.3-4.0.
Find, use the catalyzer in high tortuosity degree fixed bed device, reactant gases and catalyzer only contact the very short time and can meet the requirements of transformation efficiency.In this case, only need the seldom catalyzer of volume, this can reach the desirable high gas space velocity of operation commercial run conversely again.
Charging preferably contacts under adiabatic condition with catalyzer.In this manual, " thermal insulation " means the heat of taking away except the gas reactor effluent, and conversion zone is without any calorific loss and radiating reaction conditions.
In addition, the invention still further relates to carbon monoxide or the hydrogen that makes with aforesaid method.
The carbon monoxide of the inventive method preparation and hydrogen mixture are specially adapted to synthetic hydrocarbon (as using the Fischer-Tropsch synthesis method); Perhaps be used for synthesizing oxygen-containing thing such as methyl alcohol.Carbon monoxide and hydrogen mixture change into the method for these products and know in this area.
According to following illustrative embodiment, will further specify the inventive method, wherein embodiment 1-3 is the inventive method, embodiment 4 and 5 is in order to compare.
Embodiment 1
Preparation of catalysts
With an amount of Trichlororhodium (RhCl 3) soluble in water, make the aqueous solution that rhodium concentration is 4.12% weight.It is 3.5ml that the above-mentioned aqueous solution evaporate of 12.93g is concentrated into volume.(trilobe of 1.0mm diameter (trilobes) is available commercially, and as Dycat, 10g) is dipped in the above-mentioned solution, and the extruded stock that obtains is dry in 120 ℃ baking oven, subsequently 500 ℃ of roastings with the Alpha-alumina extruded stock.The catalyzer that obtains contains the rhodium of 5.0% weight.
Catalyzing part oxidation
Assembling contains the reactor of transparent sapphire pipe.With the crushing of the rhodium-containing catalyst of above-mentioned preparation and be loaded in the sapphire pipe, and be that the form of about 1.5 granules of catalyst fixed bed remains in the pipe with ditch Lu Zhedu.Making oxygen/carbon ratio is that 0.52 an amount of methane thoroughly mixes in entering reactor with before catalyst fixed bed the contact with oxygen.Under the pressure of 4.5 crust, with the mixture of methane and oxygen with 2,000, in the gas hourly space velocity of 000Nl/l/hr (GHSV) the adding reactor.
Service temperature with optics pyrometry measurement device catalyst bed.With gas-chromatography with the water that forms of the water vapor cooling of leaving reactor of weighing, determine to leave the composition of the gaseous mixture of reactor, measure the inventive method methane conversion and formed carbon monoxide and the selectivity of hydrogen (based on the methane that transforms).During reactor operating condition and experimental result are listed in the table below.
Embodiment 2
The method that adopts embodiment 1 to describe makes chlorination six ammonia ruthenium (III) (Ru(NH 3) 6Cl 3) aqueous solution dipping α-Al 2O 3Extruded stock prepares a kind of ruthenium-containing catalyst.The gained catalyzer contains the ruthenium of 5.0% weight.
The method that adopts embodiment 1 to describe is stated from the above-mentioned catalyzer that makes in the device and tests its activity in methyl hydride catalyzed partial oxidation.During the operational condition of reactor and experimental result are listed in the table below.
Embodiment 3
The method that adopts embodiment 1 to describe is used chloro-iridic acid (H 2IrCl 6) aqueous solution dipping α-Al 2O 3Extruded stock prepares a kind of iridium catalyst that contains.The gained catalyzer contains the iridium of 5.0% weight.
The method that adopts embodiment 1 to describe is stated from the above-mentioned catalyzer that makes in the device and tests its activity in methyl hydride catalyzed partial oxidation.During the operational condition of reactor and experimental result are listed in the table below.
Embodiment 4 comparative examples
The method that adopts embodiment 1 to describe is used Platinic chloride (H 2PtCl 6) aqueous solution dipping α-Al 2O 3Extruded stock prepares a kind of catalyst made from platonic.The gained catalyzer contains the platinum of 5.0% weight.
The method that adopts embodiment 1 to describe is stated from the above-mentioned catalyzer that makes in the device and tests its activity in methyl hydride catalyzed partial oxidation.During the operational condition of reactor and experimental result are listed in the table below.
Embodiment 5 comparative examples
The method that adopts embodiment 1 to describe is used nitric acid four ammonia palladium (II) (Pd(NH 3) 4(NO 3) 2) aqueous solution dipping α-Al 2O 3Extruded stock prepares a kind of palladium-containing catalyst.The gained catalyzer contains the palladium of 5.0% weight.
The method that adopts embodiment 1 to describe is stated from the above-mentioned catalyzer that makes in the device and tests its activity in methyl hydride catalyzed partial oxidation.During the operational condition of reactor and experimental result are listed in the table below.
In the table data as can be seen, under the temperature and pressure condition that raises, the catalyzer that contains rhodium, ruthenium or iridium shows very high stability, shows that the total conversion rate of methane is high and forms the selectivity height of carbon monoxide and hydrogen.The activity of such catalysts or the selectivity that contain rhodium, ruthenium or iridium all do not reduce significantly, all keep good performance in the entire operation process.
Under the condition of embodiment as shown in the table 1, proceeded to use the catalytic partial oxidation reaction of rhodium-containing catalyst, make total operating time reach 160 hours, do not observe catalyst activity or optionally reduction.
On the contrary, can see that the catalyzer that contains platinum or palladium shows very poor stability under used operational condition, the total conversion rate of this method and selectivity all significantly reduce.Owing on catalyzer, form coke, cause obviously increasing through the pressure drop of catalyst bed, the catalyzer service temperature obviously rises, and as shown in Table, the test of use catalyst made from platonic and palladium-containing catalyst is only carried out very short time and is just had to stop.
Table
Embodiment sequence number reactive metal 12345 rhodium ruthenium iridium platinum palladiums
The operating condition temperature (℃) 968 1,000 980 1,060 1220 pressure (bar), 4.5 3.9 4.0 3.8 3.9 GHSV (1000 Nl/l/hr), 2,000 2,000 2,000 2,000 2000 oxidations/0.52 0.52 0.52 0.52 0.52 operating time of carbon ratio (hour) 24 24 24 22
CH 4?Transformation efficiency (%) 1 81.9 73.7 77.1 66.0 60.8 CO selectivity (%) 2 91.8 80.0 84.4 70.0 69.4 H 2 Selectivity (%) 90.3 88.4 89.7 83.2 76.4
Inactivation (%) 3CH 4Transformation efficiency＜0.1＜0.1＜0.1 1.7 2.5 H 2Selectivity＜0.1＜0.1＜0.1 1.4 2.6
1 based on the CH that transforms 4, the selectivity of formation CO
2 based on the CH that transforms 4, form H 2Selectivity
3 per 1 hour operating times, the percentage that performance reduces

Claims (12)

1, the process for catalystic partial oxidation of hydrocarbon feed, this method comprise, the charging that contains hydrocarbon feed and oxygenous gas contacted in elevated pressure under with at least 950 ℃ with the catalyzer that contains catalytically-active metals rhodium, iridium or ruthenium.
According to the method for claim 1, it is characterized in that 2, described hydrocarbon feed comprises the light hydrocarbon in methane, Sweet natural gas, casing-head gas or other source.
According to the method for claim 1 or 2, it is characterized in that 3, described oxygenous gas is the oxygen of substantially pure.
4, according to the method for arbitrary requirement in the aforesaid right requirement, it is characterized in that described charging contains hydrocarbon feed and oxygenous gas, it is 0.3-0.8 that the consumption of hydrocarbon feed and oxygenous gas makes oxygen/carbon ratio, be preferably 0.45-0.75, more preferably 0.45-0.65.
5, require according to aforesaid right in the method for arbitrary requirement, it is characterized in that, to 150 crust nearly, preferred 3-100 crust, more preferably 10-75 crust, described charging is contacted with catalyzer.
6, according to the method for arbitrary requirement in the aforesaid right requirement, it is characterized in that,, preferred 950-1200 ℃, described charging is contacted with catalyzer at 950-1300 ℃.
7, according to the method for arbitrary requirement in the aforesaid right requirement, it is characterized in that the described gas hourly space velocity that contacts with catalyzer is 20,000-50,000,000Nl/l/hr is preferably 50,000-20,000,000Nl/l/hr, more preferably 500,000-10,000,000Nl/l/hr.
8, according to the method for arbitrary requirement in the aforesaid right requirement, it is characterized in that described catalyzer contains rhodium.
9, require according to aforesaid right in the method for arbitrary requirement, it is characterized in that, described catalyzer remains in the fixed bed device, preferably remains in the fixed bed device of high tortuosity degree, more preferably remains in the fixed bed device that the tortuosity degree is 1.1-5.0.
According to the method for claim 9, it is characterized in that 10, the form of described catalyzer is the ceramic foam with the catalytically-active metals dipping.
11, according to the method for arbitrary requirement in the aforesaid right requirement, it is characterized in that, under basic adiabatic condition, described charging is contacted with catalyzer.
12, according to the carbon monoxide or the hydrogen of the method for arbitrary requirement in the claim 1 to 11 preparation.
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